1. Field of the Invention
This invention relates to selective removal of organically bound sulfur from carbonaceous materials while maintaining the calorific value of the carbonaceous materials. Useful in the process of this invention are membrane fragments and enzymes from membrane fragments extracted from microorganisms, the membrane fragments and enzymes having the ability of selective cleavage of organic C--S bonds, such as from microorganisms Rhodococcus rhodochrous and Bacillus sphaericus and their derivatives. Particularly preferred are bacterial produced membrane extracts and enzymes of Rhodococcus rhodochrous ATCC No. 53968 and Bacillus sphaericus ATCC No. 53969. The process of this invention is particularly useful in removal of organic sulfur from fossil fuels, such as sulfur-containing coal and oils.
2. Description of Related Art
Sulfur content of carbonaceous fuels, such as coals and oils, has prevented utilization of a considerable amount of such materials due to deleterious effect upon the environment. Inorganic pyritic sulfur and organically bound sulfur may each constitute as much as about 3.5 weight percent or more of coal. Pyritic sulfur has been found to be relatively easy to remove by techniques including heavy media separation, selective agglomeration, flotation, jigging, magnetic separation, leaching and hydrosulfurization. Microbial metabolism of inorganic pyritic sulfur by its oxidation using bacteria such as Thiobacillus and Sulfolobus species is known. Eligwe, C. A., "Microbial Desulfurization of Coal," Fuel, 67:451-458 (1988). These chemolithotropic organisms can utilize inorganic pyritic sulfur compounds as energy sources and are capable of removing 90% or more of the inorganic pyritic sulfur from coal within a few days. Thiobacillus ferrooxidans is taught by U.S. Pat. No. 4,206,288 as suitable for removal of pyritic sulfur from coal.
Bacillus sulfasportare ATCC 39909 has been taught by U.S. Pat. No. 4,632,906 to be capable of sulfur removal from coal, without differentiation between pyritic and organic sulfur. An unidentified mixed culture of seven gram negative rods (ATCC 39327) prepared by growth in situ enriched with sulfur compounds and subsequently grown in the presence of coal has been shown to reduce the sulfur content of coal by about 20 percent per day with a substantial portion being reduction of organic sulfur as taught by U.S. Pat. No. 4,659,670.
The feasibility of theoretical concepts of enzymatic removal of organic sulfur from coal has been suggested by Ngaiza, O. G., Wise, D. L., and Gilbert, I. R., "Enzymatic Removal of Organic Sulfur from Coal," Amer. Chem. Soc. Div. Fuel them., 33(4) pages 623-630, (1988).
Removal of sulfur from petroleum hydrocarbons by contact with hydrogen in the presence of hydrogenase-producing microorganisms Desulfovibrio desulfuricans and Sporovibrio followed by removal of sulfur in the form of gaseous products is taught by U.S. Pat. No. 2,641,564. Removal of sulfur from petroleum by Pseudomonas is taught by Hartdegen, F. J., Coburn, J. M., and Roberts, R. L., "Microbial Desulfurization of Petroleum," Chem. Eng. Progress, Vol. 80, No. 5, pp. 63-67 (1984) to be by C--C cleavage. General teachings of various Pseudomonas for removal of sulfur from petroleum are in Eckart, V., Hieke, W., Bauch., J., and Gentzsch, H., "Microbial Desulfurization of Petroleum and Heavy Petroleum Fractions. 1. Studies on Microbial Aerobic Desulfurization of Romashkino Crude Oil," Zentralbl. Microbiol. 135(8), 674-681 (1980), Chemical Abstracts, Vol. 94, No. 142230q, (1981); Eckart, V., Hieke, W., Bauch, J., and Gentzsch, H., "Microbial Desulfurization of Petroleum and Heavy Petroleum Fractions. 3. Change in the Chemical Composition of Fuel-D-Oil by Microbial Aerobic Desulfurization," Zentralbl. Microbiol. 137(4), 270-279 (1982), Chemical Abstracts, Vol. 97, No. 147259c, (1982); Lee, Min Jai and Oh, Myung Soo, "Isolation, Identification, and Physiological Characteristics of Some Sulfur-Reducing Microbes," Misaengmul Hakhoe Chi, 10(4), 175-190, (1972), Chemical Abstracts, Vol. 78, No. 94605m (1973); Bauch, J., Gentzsch, H., Hieke, W., Eckart, V., Koehler, M., and Babenzin, H. D., "Oxidative Microbiological Desulfurization of Heavy Petroleum Fractions," DD Patent 108,533, 20 September (1974), Chemical Abstracts, Vol. 83, No. 82530y (1975); and Yuda, Sadayuki, " Petroleum Desulfurization by Pseudomonas haconensis," Japanese Patent 75,107,002, 23 August (1975), Chemical Abstracts, Vol. 84, No. 46982j (1976). Thiobacillus thiooxidans has been identified as the most effective S-oxidizer and Pseudomonas putrefaciens and Desulfovibrio desulfuricans the most effective S-reducers in microbial removal of sulfur from petroleum, Lee, M. J., Hah, Y. C., and Lee, K. W., "Desulfurization of Petroleum by Microorganisms. I. Isolation and Identification of Sulfur-Oxidizing and -Reducing Bacteria," Haksurwon Nonmunjip, Cha'yon Kwahak P'yon 12, 21-49, (1973), Chemical Abstracts, Vol. 85, No. 156414d (1976); Lee, M. J., Hah, Y. C., and Lee, K. W., "Desulfurization of Petroleum by Microorganisms. III. Desulfurization of Petroleum by Contact Reaction with Desulfurizing Bacteria," Haksurwon Nonmunjip, Cha'yon Kwahak P'yon 12, 73-95, (1973), Chemical Abstracts, Vol. 85, No. 145448s (1976).
Organic sulfur which is chemically bound within the carbonaceous molecule can be removed either by chemical or biological means. Dibenzothiophene (DBT) is the organo-sulfur compound most persons consider representative of the form in which organic sulfur exists in naturally occurring organic carbonaceous fuels such as coal and oil and is the compound upon which the microbial metabolism of organosulfur compounds has focused. Study of DBT metabolism has been pursued by several researchers who have isolated organisms capable of metabolizing DBT including Acinetobacter, Malik, K. A., "Microbial Removal of Organic Sulfur from Crude Oil and the Environment: Some New Perspectives," Process Biochem., 13(9), 10-13 (1978); Arthrobacter, Knecht, A. T., Jr., Thesis Dissertation, Louisiana State University, Order No. 621235 (1961); Beijerinckia, Laborde, A. L., and Gibson, D. T., "Metabolism of Dibenzothiophene by a Beijerinckia Species," Appl. Environ. Microbiol., 34, 783-790 (1977); Rhizobium, Malik, K. A., (supra); Pseudomonas, Hou, C. T. and Laskin, A. I., "Microbial Conversion of Dibenzothiophene," Dev. Ind. Microbiol., 17, 351-362 (1976); Isbister, J. D. and Kobylinski, E. A., " Microbial Desulfurization of Coal in Processing and Utilization of High Sulfur Coals," Coal Science and Technology Series, No. 9, 627, Attia, Y. A., Ed. Amsterdam: Elsevier (1985); Knecht, A. T., Jr., (supra); Kodama, K., Nakatani, S., Umehara, K., Shimizu, K., Minoda, Y., and Yamada, K., "Microbial Conversion of Petrosulfur Compounds: Isolation and Identification of Products from Dibenzothiophene," Agr. Biolog. Chem., 34, 1320-1324 (1970); Monticello, D. J., Bakker, D., and Finnerty, W. R., "Plasmid Mediated Degradation of Dibenzothiophene by Pseudomonas Species," Appl. Environ. Microbiol., 49, 756-760 (1985); Sulfolobus, Kargi, F. and Robinson, J. M., "Microbial Oxidation of Dibenzothiophene by the Thermophilic Organisms Sulfolobus acidocaldarius," Biotech. and Bioeng., 126, 687-690 (1984). The pathway of microbial degradation of DBT in each of the above cases except in Isbister, etal., (supra), is by C--C bond cleavage according to microbial degradation pathways of DBT originally established by Kodama, et al., (supra). Microbial degradation of organic sulfur-containing carbonaceous materials by C--C bond cleavage results in the loss of a large portion of the calorific value of the carbonaceous fuel. According to the Kodama, et al. (supra), C--C bond cleavage microbial degradation of DBT, sulfur-containing end products are 3-hydroxybenzothiophene sulfoxide, 2-formyl benzothiophene, or benzothiophene. A recent article, published after filing of the parent patent application, teaches degradation of dibenzothiophene resulting in carbon destruction, van Afferden, M., Schacht, S., Klein, J. and Trupper, H. G., "Degradation of Dibenzothiophene by Brevibacterium sp.DO", Arch. of Microbiol., 153, 324-328 (1990).
It is more desirable to follow a microbial degradation route which removes sulfur from the molecule without removing carbon from the molecule, thereby retaining calorific value of the fuel to a greater degree than is possible by carbon degradative pathways. Such sulfur-specific metabolism of the organic substrates requires cleavage of carbon-sulfur bonds in the organic sulfur-containing molecule. In the case of sulfur specific metabolism of dibenzothiophene, the end products are 2-hydroxybiphenyl and biomass. This C--S cleavage pathway is believed to proceed according to dibenzothiophene .fwdarw. dibenzothiophene sulfoxide .fwdarw. dibenzothiophene sulfone .fwdarw. dibenzothiophene sulfonate .fwdarw. 2-hydroxybiphenyl. The monohydroxy product of this C--S cleavage route distinguishes it from routes leading to significant amounts of dihydroxybiphenyl.
The only prior microorganism known to the present inventor allegedly capable of degradation of DBT by C--S cleavage is a Pseudomonas species as described by Isbister, (supra), and Pseudomonas ATCC 39381, as set forth in U.S. Pat. No. 4,562,156. The ATCC 39381 culture on deposit does not possess the C--S cleavage trait and the depositors of the culture have stated that the culture on deposit cannot be replaced as such cultures having the C--S cleavage trait to their knowledge do not exist. (4th Department of Energy Preparation, Utilization and Environmental Control Contractors Conference, U.S. Dept. of Energy, Pittsburgh Energy Technology Center, Pittsburgh, Pa. 15236, U.S.A., 1988). Mixed cultures obtained through growth under sulfur limited conditions have been capable of selective removal of sulfur from DBT, Kilbane, John J., "Sulfur-Specific Microbial Metabolism of Organic Compounds," Bioprocessing of Coals Workshop, Tysons Corner, Va. Aug. 16-18, 1988. A very recent article, published after filing of the parent patent application, teaches dibenzothiophene (DBT) metabolism by Corynebacterium sp. Strain SY1 and projects pathways of DBT metabolism substantially the same as those set forth for C--S bond cleavage earlier by the applicant in the parent and other earlier patent applications and patents, Omori, T., Monna, L., Saiki, Y., and Kodama, T., "Desulfurization of Dibenzothiophene by Corynebactyerium sp. Strain SY1" App. & Environ. Microbiol. 58, 3, 911-915, Mar. (1992).